JPS6271543A - Catalyst for cleaning up exhaust gas of engine - Google Patents
Catalyst for cleaning up exhaust gas of engineInfo
- Publication number
- JPS6271543A JPS6271543A JP60211640A JP21164085A JPS6271543A JP S6271543 A JPS6271543 A JP S6271543A JP 60211640 A JP60211640 A JP 60211640A JP 21164085 A JP21164085 A JP 21164085A JP S6271543 A JPS6271543 A JP S6271543A
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- exhaust gas
- agent
- layer
- coating layer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 70
- 238000004140 cleaning Methods 0.000 title abstract 2
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 39
- 239000010410 layer Substances 0.000 claims abstract description 29
- 239000007789 gas Substances 0.000 claims abstract description 22
- 239000011247 coating layer Substances 0.000 claims abstract description 21
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910000420 cerium oxide Inorganic materials 0.000 claims abstract description 12
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims abstract description 12
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 9
- 239000010948 rhodium Substances 0.000 claims abstract description 9
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000001301 oxygen Substances 0.000 claims abstract description 6
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 6
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 5
- 229910000480 nickel oxide Inorganic materials 0.000 claims abstract description 3
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000000746 purification Methods 0.000 claims description 19
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 17
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims description 2
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims description 2
- 229910000510 noble metal Inorganic materials 0.000 abstract description 4
- 239000010953 base metal Substances 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000002485 combustion reaction Methods 0.000 abstract 1
- 239000002002 slurry Substances 0.000 description 10
- 230000000694 effects Effects 0.000 description 9
- 230000007423 decrease Effects 0.000 description 8
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 3
- 239000010970 precious metal Substances 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 229910001593 boehmite Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229910052878 cordierite Inorganic materials 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 210000003754 fetus Anatomy 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000012784 inorganic fiber Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000003878 thermal aging Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Landscapes
- Catalysts (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
大発明は一内撚機関等、特に自動車から排出される排気
ガス中の一酸化炭素（以下、ＣＯという）、炭化水素（
以下、Ｉ Ｃという）および酸化窒素（以下、ＮＯｘと
いう）を低減せしめるために用いられるエンジンの排気
ガス浄化用触媒に関するものである。Detailed Description of the Invention (Field of Industrial Application) The great invention is to reduce carbon monoxide (hereinafter referred to as CO) and hydrocarbons (hereinafter referred to as CO) in the exhaust gas emitted from single-strand engines, etc., especially automobiles.
The present invention relates to an exhaust gas purifying catalyst for an engine used to reduce nitrogen oxides (hereinafter referred to as IC) and nitrogen oxides (hereinafter referred to as NOx).
（従来技術）
従来より、自動車排気ガス中のＣｏ５Ｉ−ＩＣ，ＮＯｘ
を浄化する触媒として、白金（Ｐｔ）、ロジウム（ｆｌ
ｈ）、パラジウム（Ｐｄ）等の一貴金属をアルミナ（Ａ
（ｌｔｏ３）に担持したものが用いられている。又、こ
れら貴金属の触媒性能を向上させろために、酸素貯蔵能
効果（排気ガス中の酸素を取り込み、この酸素を触媒の
浄化に寄与させる効果）がある酸化セリウム（ＣｅＯ，
）を、貴金属といっしょにアルミナコート層に含有させ
、排気ガスの浄化率を高めようとした触媒か製造されて
きている。(Prior art) Conventionally, Co5I-IC, NOx in automobile exhaust gas
Platinum (Pt) and rhodium (fl) are used as catalysts to purify
h) A noble metal such as palladium (Pd) is mixed with alumina (A
(lto3) is used. In addition, in order to improve the catalytic performance of these precious metals, cerium oxide (CeO,
) has been included in the alumina coating layer together with precious metals to improve the purification rate of exhaust gas.
しかし、貴金属および卑金属の触媒成分と、酸化セリウ
ム等の酸素貯蔵能付与剤（以下、ＯＳＣ剤という）とを
アルミナコート層に共存させて担持する方法には、以下
に述べるような問題があった。However, the method of coexisting and supporting noble metal and base metal catalyst components and an oxygen storage capacity imparting agent (hereinafter referred to as an OSC agent) such as cerium oxide on an alumina coat layer has the following problems. .
（ａ）ＯＳＣ剤と、触媒成分およびアルミとの直接的な
接触が多くなるため、Ｏ８Ｃ剤の不安定性がこれらに悪
影響をおよぼす。(a) The instability of the O8C agent adversely affects the direct contact of the OSC agent with the catalyst components and aluminum.
（ｂ）ｏｓｃ剤が触媒成分といっしょに担持されている
ため、両者が化合物をつくり、触媒成分の分散性を低下
させ、排気ガス浄化性能が低下する。(b) Since the OSC agent is supported together with the catalyst component, both of them form a compound, reducing the dispersibility of the catalyst component and reducing exhaust gas purification performance.
また、触媒担体に、ＰＬ、Ｐｄなどを含有する触媒層を
設け、該触媒層の保護のためにアルミナまたはアルミナ
と酸化セリウム（アルミナに対して重量比で０．１〜０
．５％）の混合物からなる酸化物の被覆層を設けるよう
にしたものが提案されている（特開昭６０−５２３０号
公報参照）。この公知技術の場合、微量の酸化セリウム
を含む被覆層は、触媒層を保護する目的で設けられてい
るものであり、Ｏ８Ｃ剤として作用する酸化セリウムの
濃度が極めて低いため、酸素貯蔵能効果を殆ど期待でき
ないものであった。そこで、前記被覆層のＯ８Ｃ剤含育
量を増加せしめることが考えられるが、その場合、触媒
層上が熱容量の大きなＯ９Ｃ剤担持層（換言すれば、被
覆層）に覆われることとなり、触媒層の暖気性が阻害さ
れ、低温始動時における排気ガス浄化性能が不十分とな
るおそれがある。In addition, a catalyst layer containing PL, Pd, etc. is provided on the catalyst carrier, and in order to protect the catalyst layer, alumina or alumina and cerium oxide (0.1 to 0 in weight ratio to alumina) is provided.
．． 5%) has been proposed (see Japanese Patent Laid-Open No. 60-5230). In the case of this known technology, the coating layer containing a trace amount of cerium oxide is provided for the purpose of protecting the catalyst layer, and since the concentration of cerium oxide, which acts as an O8C agent, is extremely low, it has no effect on oxygen storage capacity. It was hardly what I expected. Therefore, it may be possible to increase the O8C agent content in the coating layer, but in that case, the catalyst layer would be covered with an O9C agent supporting layer (in other words, a coating layer) with a large heat capacity, and the catalyst layer This may impede the warm-up performance of the engine, leading to insufficient exhaust gas purification performance during low-temperature startup.
（発明の目的）
本発明は、上記の問題点に鑑みてなされたもので、触媒
担体に担持されたＯ８Ｃ剤を多量に含むコート層の上面
に貴金属あるいは卑金属からなる触媒成分を含む触媒層
を形成させることにより、触媒の浄化性能（特に、低温
始動時における浄化性能）の大幅な改善を図ることを目
的とするものである。(Object of the Invention) The present invention has been made in view of the above problems, and includes a catalyst layer containing a catalyst component made of a noble metal or a base metal on the upper surface of a coat layer containing a large amount of O8C agent supported on a catalyst carrier. The purpose of this formation is to significantly improve the purification performance of the catalyst (particularly the purification performance at low temperature startup).
（目的を達成するための手段）
本発明では、上記目的を達成するための手段として、触
媒担体に担持され、ＯＳＣ剤を多量に含むコート層の上
面に、触媒成分を含有する触媒層を設けている。(Means for achieving the object) In the present invention, as a means for achieving the above object, a catalyst layer containing a catalyst component is provided on the upper surface of a coat layer supported on a catalyst carrier and containing a large amount of an OSC agent. ing.
ここで、Ｏ８Ｃ剤の成分としては、酸化セリウム（Ｃｅ
ｎｔ）、酸化ニッケル（Ｎｉｐ）、酸化モリブデン（Ｍ
ｏｂ）、酸化鉄（ＦｅｔｕｓあるいはＦｅｄ）などの公
知成分およびそれらの二種以上の混合物が使用されるが
、Ｃｅ Ｏｔが最も効果的である。Here, as a component of the O8C agent, cerium oxide (Ce
nt), nickel oxide (Nip), molybdenum oxide (M
Known components such as iron oxide (Fetus or Fed) and mixtures of two or more thereof are used, with CeOt being the most effective.
さらに、前記コート層の組成は、１０〜９５重量％のＯ
８Ｃ剤と残部の活性アルミナとするのが望ましく、その
コーティングは、Ｏ８Ｃ剤、活性アルミナ、水和アルミ
ナ、その池分散剤からなる水性スラリーを用いて行う。Furthermore, the composition of the coating layer is 10 to 95% by weight of O.
The coating is preferably an 8C agent and the remainder activated alumina, and the coating is carried out using an aqueous slurry consisting of the 08C agent, activated alumina, hydrated alumina, and a dispersant.
最も簡単な方法としては、Ｏ５Ｃ剤と水和アルミナとの
二成分を用いたスラリーをコーティングすることによっ
てコート層を形成することができる。As the simplest method, the coating layer can be formed by coating a slurry using two components: an O5C agent and hydrated alumina.
また、触媒成分としては、Ｐｔ、Ｒｈ、Ｐｄなどの公知
成分およびそれらの二種以上の混合物が使用される。Further, as the catalyst component, known components such as Pt, Rh, and Pd, and mixtures of two or more thereof are used.
かくして形成された排気ガス浄化用触媒の一例が第１図
に拡大して示されている。ここで、符号■は触媒担体、
２はコート層、３は触媒層をそれぞれ示している。該触
媒担体ｉとしては、コージライト等のセラミックスから
なるハニカム構造体あるいは耐熱金属、耐熱無機繊維よ
りなる各種担（作 用）
上記のような構造を有する触媒は、従来のように、活性
成分とＯ８Ｃ剤とを同一層に含浸せしめた触媒に比べて
非常に優れた排気ガス浄化性能を示すとともに、下層を
熱容量の大きなＯ８Ｃ剤コート層とし、上層を触媒層と
したことにより、触媒成分の暖気性が阻害されなくなり
、低温始動時の浄化性能低下が防止される。An example of the thus formed exhaust gas purifying catalyst is shown enlarged in FIG. Here, the symbol ■ is a catalyst carrier,
2 represents a coating layer, and 3 represents a catalyst layer. The catalyst carrier i may be a honeycomb structure made of ceramics such as cordierite, or various supports made of heat-resistant metal or heat-resistant inorganic fiber. In addition to exhibiting extremely superior exhaust gas purification performance compared to a catalyst impregnated with an O8C agent in the same layer, the lower layer is coated with an O8C agent with a large heat capacity, and the upper layer is a catalyst layer, which prevents warm air from the catalyst components. This prevents deterioration in purification performance during low temperature startup.
又、一般に、コート層中の一０６Ｃ剤含存量が減少する
に従って触媒性能は次第に低下し、１０％以下では急激
に低下する。その理由は、Ｏ５Ｃ剤の濃度が低下すると
、活性成分との相互作用が得られなくなるからである。Generally, as the content of the 106C agent in the coating layer decreases, the catalyst performance gradually decreases, and rapidly decreases below 10%. The reason is that as the concentration of the O5C agent decreases, no interaction with the active ingredient is obtained.
ちなみに、Ｏ８Ｃ剤としてＣｅ Ｏｔを用いたコート層
中におけるＣｅｎｔの含有量（重量％、）に対する３５
（１℃におけるＣＯの浄化率（％）の変化を測定した結
果が第２図に示されている。本結果は、活性測定条件を
、空燃比Ａ／Ｆ＝１４゜７±０．９、空間速度５Ｊ＝６
００００／ｆｉｒとし、大気中にて１１００℃で５０時
間熱エージングした後に測定したもので凧スー、′わｚ
７上わ−ぼ−ｒρＯＪ＜１１１％じＪ下ｌ二かるとＣＯ
浄化率が大幅に低下している。なお、池のｏＳＣＪｌも
これと同様な傾向を示すことは自明であろう。Incidentally, the 35
(The results of measuring the change in CO purification rate (%) at 1°C are shown in Figure 2.This result shows that the activity measurement conditions were: air-fuel ratio A/F = 14°7 ± 0.9; Space velocity 5J=6
0000/fir, and was measured after heat aging at 1100℃ in the atmosphere for 50 hours.
7 upper wa-bo-rρOJ<111% J lower l 2 Kart CO
Purification rate has decreased significantly. Note that it is obvious that the oSCJl of ponds also shows a similar tendency.
一方、Ｏ８Ｃ剤の含有量が高くなると、触媒活性は向上
するが、Ｏ８Ｃ剤自体の結合力が弱いために、物理的強
度（耐剥離性）が減少し、耐久性が低減する。ちなみに
、Ｏ８Ｃ剤としてＣｅ Ｏｔを用いたコート層中におけ
るＣ ｅ Ｏ２の含有量（重重％）を変化させて、剥離
テストを行ったところ、表−１に示す結果が得られた。On the other hand, when the content of the O8C agent increases, the catalytic activity improves, but since the binding force of the O8C agent itself is weak, the physical strength (peeling resistance) decreases and the durability decreases. Incidentally, when a peel test was conducted by varying the content (weight %) of CeO2 in the coating layer using CeOt as the O8C agent, the results shown in Table 1 were obtained.
ここで、剥離量＝（テスト前のコート付着量−テスト後
のコート付着！り／（テスト前のコート付着量）、また
、テスト方法としては、直径１インチ、高さ１インチの
円筒テストピースを６００℃で３０分間加熱、次に２５
℃の水中で冷却という手順を三日繰り返した後、充分乾
燥し、剥離量を測定する方法が採用された。Here, the amount of peeling = (Coat adhesion amount before test - Coat adhesion after test! / (Coat adhesion amount before test)) Also, as a test method, use a cylindrical test piece with a diameter of 1 inch and a height of 1 inch. Heated at 600℃ for 30 minutes, then heated at 25℃ for 30 minutes.
After repeating the procedure of cooling in water at ℃ for three days, it was thoroughly dried and the amount of peeling was measured.
表−１
上記剥離テストの結果から、コート層中のＣｅ０、含有
量は、９５％以下とするのが好ましいことがわかる。な
お、他のＯ８Ｃ剤もこれと同様な傾向を示すことは自明
であろう。Table 1 From the results of the above peel test, it can be seen that the Ce0 content in the coating layer is preferably 95% or less. Note that it is obvious that other O8C agents also exhibit a similar tendency.
前記コート層の触媒担体に対する付着割合が３重量％以
下では低濃度すぎ、上層の触媒成分の性能向上が表れな
いため、触媒性能が急激に低下し、４０重量％を越えて
も、触媒性能向上に寄与しなくなり、且つコート層の物
理的強度が低下し、剥離しやすくなる。このことを勘案
すると、コート層の付着割合を３〜４０重量％とするの
が望ましい。If the adhesion ratio of the coat layer to the catalyst carrier is less than 3% by weight, the concentration is too low and no improvement in the performance of the catalyst components in the upper layer is seen, resulting in a rapid decline in catalytic performance.Even if it exceeds 40% by weight, the catalytic performance will not improve. In addition, the physical strength of the coating layer decreases, making it easier to peel off. Taking this into consideration, it is desirable that the adhesion ratio of the coating layer be 3 to 40% by weight.
以下、本発明の好適な実施例を説明する。Hereinafter, preferred embodiments of the present invention will be described.
実施例
酸化セリウム４００ｇ、ベーマイト１００ｇ、水５５０
ｃｃをホモミキサーにより混合撹拌し、Ｏ８Ｃ剤コート
用スラリーを得た。このスラリーに、ノに°カム触媒担
体（コージライト製）を浸漬して引き上げた後、余分の
スラリーを高圧エアブロ−で除去し、昇温速度２００℃
／Ｉｌｒにセットした電気炉中に置いて３３０〜５５０
℃の温度で１時間焼成した。これにより、酸化セリウム
８２重機％、活性アルミナ１８重量％からなるコート層
を触媒担体に対して２０重量％コーティングすることが
できた。Example cerium oxide 400g, boehmite 100g, water 550g
cc was mixed and stirred using a homomixer to obtain a slurry for coating with an O8C agent. A cam catalyst carrier (made of cordierite) was immersed in this slurry and pulled up, and the excess slurry was removed with a high-pressure air blower.
/Ilr in an electric furnace set to 330-550
It was baked for 1 hour at a temperature of °C. As a result, it was possible to coat the catalyst carrier with a coating layer consisting of 82% cerium oxide and 18% activated alumina by 20% by weight.
次いで、γ−アルミナ１６０ｇ、ベーマイト１６０ｇ。Next, 160 g of γ-alumina and 160 g of boehmite.
水５００ｃｃ、ｆｉ硝酸４ｃｃをホモミキサーによりＩ
Ｏ時間混合撹拌し、アルミナウォッシュコート用スラリ
ーを得た。このスラリーに、先のＯ８Ｃ剤コーティング
済みの触媒担体を浸漬して引き上げた後、余分のスラリ
ーを高圧エアブロ−で除去し、２００℃／１１ｒの昇温
速度で２００〜６００℃で焼成した。次ぎに、これを所
定の濃度の塩化白金酸・塩化ロジウム混合水溶液に浸漬
して引き上げた後、２００℃で１時間乾燥し、５５０℃
で２時間焼成した。焼成後の貴金属含有ｆｆｉハ白金（
Ｐ Ｌ）１．Ｏｇ／ ＋１ 、ロジウム（Ｒｈ）０．２
ｇ／ １１ テあった。500cc of water and 4cc of fi nitric acid were added using a homomixer.
The mixture was mixed and stirred for 0 hours to obtain an alumina washcoat slurry. After the catalyst carrier coated with the O8C agent was immersed in this slurry and pulled up, excess slurry was removed by high-pressure air blowing, and the carrier was calcined at 200 to 600°C at a heating rate of 200°C/11r. Next, this was immersed in a mixed aqueous solution of chloroplatinic acid and rhodium chloride of a predetermined concentration, pulled up, dried at 200°C for 1 hour, and then heated to 550°C.
It was baked for 2 hours. Precious metal-containing ffi after firing is platinum (
P L)1. Og/ +1, rhodium (Rh) 0.2
There was g/11 te.
上記実施例で得られた排気ガス浄化用触媒の浄化性能を
、従来公知の触媒、即ち、触媒活性成分とＯ８Ｃ剤とを
混在せしめてなる触媒と比較して評価テストを行ったと
ころ、第３図ないし第５図に示す結果が得られた。ここ
で、比較例は次のトへに１１咽制太バナー
比較例
活性アルミナ１００ｇ、酸化セリウム４００ｇ、濃硝酸
４Ｃｃ１水７０Ｇｃｃをホモミキサーにより混合撹拌し
、アルミナ及びＯ８Ｃ剤コート用のスラリーを得た。An evaluation test was conducted to compare the purification performance of the exhaust gas purification catalyst obtained in the above example with a conventionally known catalyst, that is, a catalyst made by mixing a catalytic active component and an O8C agent. The results shown in Figures 5 through 5 were obtained. Here, the comparative example is as follows: 11 Thick Banner Comparative Example 100 g of activated alumina, 400 g of cerium oxide, 4 Cc of concentrated nitric acid, and 70 Gcc of water were mixed and stirred using a homomixer to obtain a slurry for alumina and O8C agent coating. .
このスラリーを用いて、前記実施例と同一方法でハニカ
ム触媒担体にアルミナ及びＯ８Ｃ剤をコーティングした
。このコート層の付着量は触媒担体に対して２５重量％
、酸化セリウムのコート層中での割合は８２重量％であ
った。Using this slurry, a honeycomb catalyst carrier was coated with alumina and an O8C agent in the same manner as in the previous example. The amount of this coating layer attached is 25% by weight based on the catalyst carrier.
The proportion of cerium oxide in the coating layer was 82% by weight.
この触媒担体にさらに前記実施例と同様な方法を用イテ
、白金（ＰＬ）１．ｏｇ／１１、ロジウム（Ｒｈ）０．
２ｇ／（ｌを付着させることにより触媒に調製した。This catalyst carrier was further coated with platinum (PL) using the same method as in the previous example. og/11, rhodium (Rh) 0.
The catalyst was prepared by depositing 2 g/(l).
なお、活性測定条件を、空燃比Ａ／Ｐ＝１４．７±０．
９、空間速度Ｓ、 ％’６００００／ｌｌｒとし、大気
中１１００℃でｌＯ時間熱エージング後に測定したもの
である。The activity measurement conditions were air-fuel ratio A/P=14.7±0.
9. Space velocity S, %'60000/llr, measured after thermal aging at 1100° C. for 10 hours in the atmosphere.
上記評価テストの結果によると、本発明の実施例による
排気ガス浄化用触媒は、従来公知の触媒、即ち、比較例
のものに比較して大幅に浄化性能が改善されていること
がわかる。特に、低温域において、触媒活性が良好にな
っているが、これは、ｏＳＣ剤コート層を触媒層の下層
に位置させたことにより、触媒層の暖気性が向上したこ
とによる。According to the results of the above evaluation test, it can be seen that the exhaust gas purifying catalyst according to the example of the present invention has significantly improved purification performance compared to the conventionally known catalyst, that is, the comparative example. Particularly in the low temperature range, the catalyst activity is good, and this is due to the fact that the oSC agent coating layer is located below the catalyst layer, which improves the warming properties of the catalyst layer.
（発明の効果）
層上の如く 、本発明によれば、ＯＳＣ剤（ＣｅＯ，、
ＮｉＯ等）を含有するコート層上に活性触媒成分（Ｐｔ
、Ｒｈ、Ｐｄ等）を含有する触媒層を形成しているので
、活性触媒成分とＯ８Ｃ剤とが化合物を形成することが
なくなり、従来の活性触媒成分とＯ８Ｃ剤とを混在させ
たものに比べて、排気ガス浄化性能が向上するとともに
、活性触媒成分が排気ガスの低温域から有効に反応し、
コールドスタート時における浄化性能を著しく向上させ
ることができるいう優れた効果がある。(Effects of the Invention) According to the present invention, the OSC agent (CeO,...
An active catalyst component (Pt
, Rh, Pd, etc.), the active catalyst component and the O8C agent do not form a compound, compared to the conventional combination of the active catalyst component and the O8C agent. As a result, exhaust gas purification performance is improved, and the active catalyst component reacts effectively from the low temperature range of exhaust gas.
This has the excellent effect of significantly improving purification performance at the time of cold start.
また、比較的耐熱性に劣るＯ８Ｃ剤を含むコート層が触
媒層の下層に形成されているため、該コート層の熱劣化
を低減せしめることができるという効果もある。Furthermore, since the coat layer containing the O8C agent, which has relatively poor heat resistance, is formed below the catalyst layer, there is also the effect that thermal deterioration of the coat layer can be reduced.
さらに、実施態様項の如く、Ｏ８Ｃ剤のコート層中にお
ける含有量を１０〜９５重量％とすれば、０ＳＣ剤によ
る酸素貯蔵能効果が大幅に増大せしめられることとなり
、排気ガス浄化性能をさらに向上せしめることができる
という効果か得られる。Furthermore, as in the embodiment section, if the content of the O8C agent in the coating layer is 10 to 95% by weight, the oxygen storage capacity effect of the OSC agent will be greatly increased, further improving the exhaust gas purification performance. You can get the effect of being able to encourage people.
第１図は、本発明にかかる排気ガス浄化用触媒の一例を
示す拡大図、第２図は、本発明にかかる排気ガス浄化用
触媒におけるコート層中のＣｅ Ｏ２含有量（重量％）
に対する排気ガス中のＣＯ／！化率（％）の変化を示す
特性図、第３図、第４図及び第５図は、本発明の実施例
と比較例との浄化性能評価テストの結果を示す特性図で
ある。
ｌ・・・・・触媒担体
２・・・・・コート層
３・・・・・触媒層
排気ガス温度（’ｃ）
排気ガス温度（’ｃ）Fig. 1 is an enlarged view showing an example of the exhaust gas purification catalyst according to the present invention, and Fig. 2 shows the Ce O2 content (wt%) in the coat layer of the exhaust gas purification catalyst according to the present invention.
CO/! in the exhaust gas against! 3, 4, and 5 are characteristic diagrams showing the results of a purification performance evaluation test of an example of the present invention and a comparative example. l... Catalyst carrier 2... Coating layer 3... Catalyst layer exhaust gas temperature ('c) Exhaust gas temperature ('c)
Claims (1)
する酸化セリウム、酸化ニッケル、酸化モリブデンおよ
び酸化鉄よりなる群から選ばれた少なくとも一種類の酸
化物を含有するアルミナのコート層と、該コート層上に
設けられ、白金、ロジウムおよびパラジウムよりなる群
から選ばれた少なくとも一種類の触媒成分を含有する触
媒層とを備えていることを特徴とするエンジンの排気ガ
ス浄化用触媒。 ２、前記コート層における酸素貯蔵能付与剤含有量が１
０〜９５重量％とされている前記特許請求の範囲第１項
記載のエンジンの排気ガス浄化用触媒。[Claims] 1. Alumina supported on a catalyst carrier and containing at least one oxide selected from the group consisting of cerium oxide, nickel oxide, molybdenum oxide, and iron oxide, which acts as an oxygen storage ability imparting agent. and a catalyst layer provided on the coat layer and containing at least one catalyst component selected from the group consisting of platinum, rhodium, and palladium. Purification catalyst. 2. The content of the oxygen storage ability imparting agent in the coating layer is 1
The catalyst for purifying exhaust gas of an engine according to claim 1, wherein the catalyst content is 0 to 95% by weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60211640A JPH0622675B2 (en) | 1985-09-24 | 1985-09-24 | Engine exhaust gas purification catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60211640A JPH0622675B2 (en) | 1985-09-24 | 1985-09-24 | Engine exhaust gas purification catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6271543A true JPS6271543A (en) | 1987-04-02 |
| JPH0622675B2 JPH0622675B2 (en) | 1994-03-30 |
Family
ID=16609122
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60211640A Expired - Fee Related JPH0622675B2 (en) | 1985-09-24 | 1985-09-24 | Engine exhaust gas purification catalyst |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0622675B2 (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63256141A (en) * | 1987-04-11 | 1988-10-24 | Mazda Motor Corp | Catalyst for purifying exhaust gas |
| JPS63310637A (en) * | 1987-06-12 | 1988-12-19 | ジヨンソン マセイ インコ−ポレ−テツド | Triple effective catalyst |
| JPH01143640A (en) * | 1987-10-26 | 1989-06-06 | Ford Motor Co | Noble metal-containing oxidizing catalyst supported by alumina, and its production and use |
| JPH02198635A (en) * | 1989-01-26 | 1990-08-07 | Matsushita Electric Ind Co Ltd | Catalyst for cleaning exhaust gas |
| US6620762B2 (en) | 2000-07-18 | 2003-09-16 | Daihatsu Motor Co., Ltd. | Exhaust gas purifying catalyst |
| US6864214B2 (en) | 2000-09-26 | 2005-03-08 | Daihatsu Motor Co., Ltd. | Exhaust gas purifying catalyst |
| JP2007530277A (en) * | 2004-03-30 | 2007-11-01 | エンゲルハード・コーポレーシヨン | Exhaust gas treatment catalyst |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6178439A (en) * | 1984-09-26 | 1986-04-22 | Kiyataraa Kogyo Kk | Catalyst for purifying exhaust gas |
-
1985
- 1985-09-24 JP JP60211640A patent/JPH0622675B2/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6178439A (en) * | 1984-09-26 | 1986-04-22 | Kiyataraa Kogyo Kk | Catalyst for purifying exhaust gas |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63256141A (en) * | 1987-04-11 | 1988-10-24 | Mazda Motor Corp | Catalyst for purifying exhaust gas |
| JPS63310637A (en) * | 1987-06-12 | 1988-12-19 | ジヨンソン マセイ インコ−ポレ−テツド | Triple effective catalyst |
| JPH01143640A (en) * | 1987-10-26 | 1989-06-06 | Ford Motor Co | Noble metal-containing oxidizing catalyst supported by alumina, and its production and use |
| JPH02198635A (en) * | 1989-01-26 | 1990-08-07 | Matsushita Electric Ind Co Ltd | Catalyst for cleaning exhaust gas |
| US6620762B2 (en) | 2000-07-18 | 2003-09-16 | Daihatsu Motor Co., Ltd. | Exhaust gas purifying catalyst |
| US6864214B2 (en) | 2000-09-26 | 2005-03-08 | Daihatsu Motor Co., Ltd. | Exhaust gas purifying catalyst |
| JP2007530277A (en) * | 2004-03-30 | 2007-11-01 | エンゲルハード・コーポレーシヨン | Exhaust gas treatment catalyst |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0622675B2 (en) | 1994-03-30 |
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| LAPS | Cancellation because of no payment of annual fees |